CN101155892A - Stabilized iodocarbon compositions - Google Patents

Abstract

Disclosed are compositions comprising at least one iodocarbon compound and preferably at least one stabilization agent comprising a diene-based compound. These compositions are generally useful as refrigerants for heating and cooling, as blowing agents, as aerosol propellants, as solvent composition, and as fire extinguishing and suppressing agents.

Description

Stable iodocarbon compositions

Technical field

Do not have

Background technology

Halohydrocarbon has been widely used in the multiple industrial application, comprises as refrigeration agent, aerosol propellant, whipping agent, heat-transfer medium and gaseous dielectric.Up to now, great majority had utilized the composition that comprises a large amount of Chlorofluorocarbons (CFCs) (" CFC ") and Hydrochlorofluorocarbons (" HCFC ") during these were used.Yet, suspect that the use of some of them halohydrocarbon has caused environmental problem.For example, CFC tends to show relative higher global warming potential (global warmingpotential) with HCFC.Therefore, in many application, need to use desired use to accept, but the while global warming potential is than CFC and the low composition of other unfavorable halogenated compound.

The applicant has recognized that, in refrigeration (and other) is used, may advantageously use some to comprise the composition of iodo compound, and the composition that especially comprises CF3I, substitute various chlorinated compounds (wherein many all have high global warming potential), so that reduce the latency environment infringement that causes because of high global warming potential.Yet the applicant also recognizes in addition, and for example the iodo compound of CF3I tends to unstablely relatively, and stability often significantly is lower than CFC, HCFC and hydrogen fluorohydrocarbon (HFC), especially under some conventional refrigeration condition.

For as refrigeration agent and other CFC, HCFC and HFC fluidic substitute, must make the suitable groups compound stabilization that comprises iodo compound.The applicant has recognized that a kind of mode that may produce suitable stable iodo-containing composition is to use stable compound therein.

Become known for the various stablizers of HCFC and CFC composition.Known as affiliated field, HFC may use owing to have superior stability or may not use the stablizer of incorporating in its composition.For example, United States Patent (USP) the 5th, 380 discloses at least a phenol that comprises dichlorotrifluoroethane and stable quantity and the composition of at least a aromatic series or fluoro-alkyl epoxide for No. 449.Yet, tend to significantly be lower than CFC and HCFC because contain iodine compound stability, so whether can contain the degree that iodine compound is stabilized to be enough to as the CFC/HCFC substitute from the unpredictable same or analogous compound of instruction (for example the ' No. 449 specification sheetss) about the stablizer of CFC and HCFC.In other words, recognize that C-Cl and C-F key tend to than at least firmly about 1.5-2 of C-I key doubly as the those skilled in the art.Therefore, expection make HCFC or the stable compound of CFC also be applicable to stability need approximately to increase twice and be used for refrigerant applications to contain iodine compound be irrational at all or also to there is no need be rational.

Therefore, the applicant has recognized that to need to produce and enough stablizes to be used to comprise the multi-purpose composition that contains iodine compound (for example CF3I) that comprises as CFC, HCFC and HFC refrigeration agent substitute.

Someone proposes to utilize in refrigeration application some iodine hydrocarbon (iodocarbon) compound as some used before this CFC and the substitute of HCFC.For example, the open 09-059612 (application case 07-220964 number) of Japan's special permission discloses the refrigerant composition that comprises CF3I and one or more phenolic compounds.This patent document shows that the phenols composition plays a part to stablize CF3I in case degraded.

May obtain certain effect though contain phenolic compound as the composition of CF3I stablizer, may not wish to use phenolic compound in some applications, perhaps wish to use the phenolic compound of low concentration.For example, because the dissociable property of hydroxyl, it is acid that phenols is usually, and have relative reactivity.These features may be disadvantageous under some application and/or some situation.

Summary of the invention

The invention provides and comprise iodine hydrocarbon compound (for example, CF3I, CF ₃I) multiple composition, described composition are stablized unusually and can be advantageously used in the multiple application, comprise as the refrigeration agent in the various cooling systems.Specifically, the applicant is unexpected to be found, the iodine hydrocarbon compound, common C1-C5 iodine hydrocarbon, and even more preferably C1-C2 iodine hydrocarbon (for example preferred C1 iodine hydrocarbon CF3I) can combine generation with one or more various stabilizer compounds and is applicable to commerce, industry or personal use, and especially, be preferably the composition that contains CF3I as the stable iodocarbon compositions that contains of heat-transfer fluid in refrigeration system, air-conditioning system (comprising automotive air-conditioning system) and the similar system.In addition, composition of the present invention is not only enough stable being used for multiple use, and tends to show the unique combination of non-inflammability and low-ozone loss and Global warming characteristic, makes it become the material standed for that CFC, HCFC and HFC refrigeration agent substitute are particularly useful.

Therefore, in one embodiment, the present invention is directed to the composition that comprises at least a iodine hydrocarbon compound (preferred C1-C5 iodine hydrocarbon, and even more preferably C1 iodine hydrocarbon) and at least a stable compound.Expect that described in some cases composition may comprise based on any one or more than one stablizer in the stablizer classification of free radical scavenging functional group, but in many preferred embodiments, stablizer comprises, and preferably comprise the dialkylene compound with vast scale at least, and even more preferably comprise the isoprene based compound.Term " dialkylene compound " is meant C3-C5 diene, the compound that can form by the reaction that relates to the C3-C5 diene as used herein.Term " isoprene based compound " is meant isoprene, has the compound of isoprene part and the compound that can form by the reaction that relates to isoprene as used herein.For example, definite diolefin as used herein comprises myrcene (myrcene) and farnesol (farnesol), and these two all has three carbon-carbon double bonds.Therefore, term " dialkylene " is not limited to only to have the compound of two two keys, and comprises having and be less than or the compound of a plurality of two carbon-carbon double bonds.Under the situation of the dialkylene compound that is combined to form by the C3-C5 diene, the molecule of combination can be identical or different.Term " iodine hydrocarbon " is meant any compound that contains at least one carbon iodine key as used herein, and be intended to contain the iodine fluorohydrocarbon and (have at least one carbon iodine key and at least one carbon-fluorine bond, and the compound of other key of nothing except that carbon-carbon bond) and hydrogen iodine fluorohydrocarbon (have at least one carbon iodine key, at least one carbon-fluorine bond, at least one hydrocarbon key, and do not have the compound of other key except that carbon-carbon bond).

The applicant has recognized that under some working conditions, iodine hydrocarbon compound stability tends to be lower than the compound with C-Cl and C-F key replaced C-I key usually.Therefore, the applicant also recognizes need provide enough stable to be used for the composition that comprises iodine hydrocarbon compound (for example CF3I) of various uses, comprises the substitute as CFC and HCFC refrigeration agent.The present composition can reduce the environmental damage that will cause when using CFC and HCFC based composition and use thereof in packaging instead.Yet the applicant recognizes also that in addition iodo compound tends to unstable relatively usually, and under some working conditions, for example under the existence conditions of conventional refrigeration system, stability significantly is lower than CFC and HCFC usually.For example, when ASHRAE that various refrigeration agents are recommended and SAE standard testing, present inventor's discovery comprises the iodine of the compound generation palm fibre/black of iodine fluorohydrocarbon, thinks that this is formed by the degraded of iodine fluorohydrocarbon under test condition.

The present inventor is surprised to find that, the iodine hydrocarbon compound, preferred C1-C2 iodine hydrocarbon, more preferably C1 iodine hydrocarbon, and even more preferably CF3I, can be with at least a stable compound, preferably have a compound of free radical scavenging functional group, and even more preferably at least a dialkylene compound be applicable to the stable composition of multiple application in conjunction with generation.In addition, composition of the present invention is not only enough stable to be used for multiple use, but also tend to show the unique combination of non-inflammability and low-ozone loss characteristic, make it especially be suitable as heat-transfer fluid, especially be used as candidate's substitute of present used refrigeration agent, for example CFC and HCFC refrigeration agent substitute.In addition, the applicant finds, except that the iodine hydrocarbon, and the composition that preferably also comprises stablizer, one or more other compounds (especially comprising HFC (preferred C1-C4HFC) and haloolefin (preferably C2-C5 haloolefin)) can reach according to many advantages of the present invention.

The applicant recognizes that in addition preferred composition of the present invention is stable and is applicable to multiple systems, apparatus and method.For example, one aspect of the present invention provides system, the apparatus and method that comprise as the present composition of heating or cooling fluid (based on latent heat transmission and/or sensible heat transfer), for example in refrigeration application, especially comprises the automative air conditioning application.As explaining more comprehensively that hereinafter the present invention also comprises other system, apparatus and method.

On the other hand, the invention provides the mthods, systems and devices that stablizer used according to the invention makes (preferably comprising the dialkylene compound) composition stable that comprises at least a iodine hydrocarbon compound.

Description of drawings

Do not have

Embodiment

I. composition-general introduction

Preferred compositions comprises at least a iodine hydrocarbon, preferred C1 iodine fluorohydrocarbon (CF3I (CF for example ₃And preferably also comprise and preferablely under working conditions, effectively stablize the iodine hydrocarbon I)), in case at least a stablizer of the amount of degrading is preferably the dialkylene compound.

Some preferred composition of the present invention comprises iodine hydrocarbon and at least a C2-C5 haloolefin, preferred C2-C4 haloolefin, and even more preferably have a C2-C4 haloolefin of at least two and preferred at least three fluoro substituents.The particularly preferred haloolefin that can be used in combination with the heat transfer applications of for example automative air conditioning in the described haloolefin is a tetrafluoeopropene, especially is 2,3,3,3-tetrafluoeopropene (HFO-1234yf).In described some preferred embodiment, gross weight in iodine hydrocarbon and haloolefin, it is about 20% to about 40% iodine hydrocarbon that described composition comprises weight percent, 25% to about 35% iodine hydrocarbon more preferably from about, with weight percent be about 60% to about 80% C2-C4 haloolefin, and even 65% to about 75% haloolefin more preferably from about.

Some preferred composition of the present invention comprises iodine hydrocarbon and at least a C1-C4HFC, preferred C1-C3HFC, and even more preferably C1-C2HFC.In described some preferred embodiment, gross weight in iodine hydrocarbon and HFC, it is about 50% to about 95% iodine hydrocarbon that described composition comprises weight percent, 65% to about 85% iodine hydrocarbon more preferably from about, with weight percent be about 5% to about 50% HFC, and even 15% to about 35% HFC more preferably from about.

In a preferred embodiment, the present composition have be not more than about 1000, more preferably no more than about 500 and even more preferably no more than about 150 and be not more than about 100 global warming potential (GWP) in some cases.In certain embodiments, the GWP of the present composition is not more than about 75.Such as in the report " The Scientific Assessment of Ozone Depletion " (incorporating this paper by reference into) of the world in 2002 meteorological association whole world ozone research and monitoring plan (World Meteorological Association ' s Global Ozone Research and Monitoring Project) definition, " GWP " used herein is with respect to carbonic acid gas " GWP " and measure in 100 year scopes.

And it is about 0.05 that the ozone depletion latent energy value (ODP) of described composition preferably is not more than, more preferably no more than about 0.02 and be even more preferably about 0.In report " TheScientific Assessment of Ozone Depletion " (incorporating this paper by reference into) literary composition of the world's meteorological association whole world ozone research in 2002 and monitoring plan " ODP " used herein defined.。

A. iodine hydrocarbon

In view of the instruction of this paper, expect that iodine hydrocarbon compound of the present invention may comprise one or more in multiple this compounds.For example, be expected in some preferred embodiment, the iodine hydrocarbon compound is a C1-C6 iodine hydrocarbon, and even C1-C3 iodine fluorohydrocarbon more preferably.The iodine hydrocarbon can be formed by carbon, hydrogen, fluorine and iodine.

In some preferred composition of the present invention, the iodine hydrocarbon comprises C1-C3 iodine hydrocarbon, more preferably C1 iodine hydrocarbon, and even more preferably C1 iodine fluorohydrocarbon.In some particularly preferred embodiment, described at least a iodine hydrocarbon compound comprises, and preferably comprises the CF3I (CF that accounts for larger proportion in iodine hydrocarbon compound total amount ₃I).Therefore, in some particularly preferred embodiment, composition of the present invention comprises at least a C1 compound that contains carbon-fluorine bond and carbon-iodine bond, wherein even more preferably contains the C1 compound of at least two carbon-fluorine bonds and at least one carbon-iodine bond.

CF3I is easy to buy from multiple commercial source, comprises Matheson TriGas, Inc..In addition, can use the CF3I for preparing through any ordinary method.Albert L.Henne and William G.Finnegan are at JACS72,3806 (1950), " The Degradation of Silver Trifluoroacetate to Trifluoroiodomethane " discloses an example among the conventional preparation method of CF3I in (incorporating this paper by reference into).

In general, the amount of iodine hydrocarbon compound in composition can extensively change, and this depends on multiple factor, for example comprises the particular desired condition of using compound.In some preferred embodiment, the weight percent content of iodine hydrocarbon compound in the present composition is about 10% to less than about 100%, and more preferably from about 20% to less than about 100%.In some preferred embodiment, especially contain among the embodiment of HFC at described composition, the weight percent content of iodine hydrocarbon compound in the present composition is about 35% to about 95%, and more preferably from about 45% to about 95%, and even more preferably from about 65% to about 95%.In some preferred embodiment, especially contain among the embodiment of haloolefin at described composition, the weight percent content of iodine hydrocarbon compound in the present composition is about 15% to about 50%, and more preferably from about 20% to about 40%, and even more preferably from about 25% to about 35%.

Relative weight about iodine hydrocarbon compound and stablizer, in certain embodiments, gross weight by iodine hydrocarbon and stablizer in the composition (preferred dialkylene compound), the weight percent content of iodine hydrocarbon is about 90% to about 99.999%, more preferably about 95% to about 99.99%, and even more preferably about 96% to about 99.7%.

B. dialkylene compound

Expect any or more than one commercially available dialkylene compound all is applicable to the present invention, and in view of the instruction of this paper, the those skilled in the art should be able to be in the quantity and the type of the described compound of selecting to be applicable to any special applications invariably under the situation of experiment.The type of dialkylene compound to be used and character are somewhat dependent upon the special iodine hydrocarbon compound that uses in the described composition, the expection working conditions and the correlative factor of composition at least.

Usually the consumption of dialkylene stablizer can extensively change in the expection present composition, and this depends on multiple factor, for example the expection working conditions of the type of iodine hydrocarbon, composition and other correlative factor in the composition.In general, preferably use with respect to the dialkylene stablizer of used iodine hydrocarbon as significant quantity.Produce the amount of the dialkylene compound of stable composition when term " significant quantity " is meant in joining the composition that comprises relevant iodine hydrocarbon compound (for example CF3I) as used herein, in described stable composition, with respect under identical or conditions of similarity, but the same combination when not having the dialkylene compound, the iodine hydrocarbon is degraded more lentamente and/or on littler degree.In the particular example of CF3I, a kind of important degradation production is a trifluoromethane, and this is to replace CF by hydrogen ₃Iodine in the I molecule forms.Similarly, hydrogen can replace the iodine in other iodine hydrocarbon, thereby forms the compound of GWP value higher relatively (for example greater than 150).These degradation productions can increase the GWP of the refrigerant blend of using the iodine hydrocarbon.Therefore can not realize having the target of low global warming potential.Effective amount of stabilizer preferably will reduce the decomposition amount of iodine hydrocarbon, so that the GWP of refrigerant composition is lower than 1000, and even be more preferably less than 150.Even do not consider the GWP value, the decomposition of component also is disadvantageous in the refrigerant composition.Therefore, by the total amount of refrigerant composition, the weight percent content of above-mentioned degradation production is preferably less than 2.0%, is more preferably less than approximately 1.0%, and even is more preferably less than about 0.5%.In some preferred embodiment, the amount of dialkylene compound is enough to produce stable composition, in described stable composition, when according to SAE J1662 (in June, 1993 promulgation) and/or ASHRAE 97-1983R (promulgation in 1997) standard test test, the same combination of at least a iodine hydrocarbon compound wherein when not having the dialkylene compound,, degrade more lentamente and/or on littler degree.For example, in some preferred embodiment, composition is being maintained at about under 300  after about two weeks, the weight percent content of degradation production (promptly replacing the formed product of iodine in the iodine hydrocarbon by hydrogen) is less than about 0.9%, and even more preferably less than about 0.7%.

In some preferred embodiment, with the described composition (composition that preferably comprises the iodine hydrocarbon, and the gross weight meter refrigerant composition that more preferably comprises the iodine hydrocarbon), the weight percent content of dialkylene compound in described composition is about 0.001% to about 15%, more preferably about 0.01% to about 10%, and even more preferably about 0.3% to about 5%, and even more preferably about 1 to about 2%.In some cases, gross weight in lubricant and stablizer, the weight percent content of dialkylene compound in described composition is about 0.001% to about 15%, more preferably about 0.01% to about 10%, and even more preferably about 0.3% to about 5%, and even more preferably about 1 to about 2%.In some preferred embodiment, in the gross weight of composition (composition that preferably comprises the iodine hydrocarbon), the weight percent content of dialkylene compound is about 0.5% to about 2%.

Dialkylene compound of the present invention can be ring-type or non-annularity, wherein common in many examples first-selected open chain compound.Be used for non-annularity dialkylene compound of the present invention and be preferably C5-C30 dialkylene compound, C5-C20 dialkylene compound more preferably, and even C5-C15 dialkylene compound more preferably.For the cyclic diene based compound, described compound can be aromatic series or non-aromatic, wherein first-selected in certain embodiments non-aromatic dialkylene ring compound.

In a preferred embodiment, the dialkylene compound is selected from the group that is made up of following each thing: allyl ethers, propadiene, divinyl, isoprene based compound (comprise two or more combination arbitrarily in terpenes (for example myrcene) and terpene derivatives (for example farnesol and Geraniol) and these compounds.As used herein, each compound of confirming in the previous list all comprise confirm compound be substituted and be unsubstituted form.In some preferred embodiment, the dialkylene compound comprises the propadiene that accounts for exhausted vast scale, and even more preferably is made up of propadiene basically.

In some other preferred embodiment, the dialkylene compound comprises terpenes, terpene derivatives or the described combination of compounds that accounts for exhausted vast scale, and even more preferably is made up of terpenes, terpene derivatives or described combination of compounds basically.Term " terpenes " expression comprises at least ten carbon atoms and contains at least one and the compound of preferred at least two isoprene part as used herein.In many preferred embodiments, (CH2=C (CH3)-CH=CH2) (each unit can be substituted or be unsubstituted) reacts and forms terpene compound of the present invention, and therefore many terpene compounds of the present invention all preferably have at least 10 carbon atoms and comprise at least one isoprene part by at least two isoprene C5 unit.Term " isoprene part " is meant that comprise can be by any molecular moiety that is substituted or is unsubstituted the group that isoprene forms as used herein.The first-selected terpenes that is unsubstituted in some preferred embodiment.

In many preferred embodiments, terpene compound of the present invention comprises through upgrading or without at least a condensation product end to end of upgrading isoprene molecule.Expect any or more than one terpene compound all is applicable to the present invention, and in view of the instruction of this paper, the those skilled in the art should be able to be in the quantity and the type of the terpene compound of selecting to be applicable to any special applications invariably under the situation of experiment.Preferred terpenes of the present invention be ring-type or non-annularity, saturated or unsaturated, be substituted or be unsubstituted structure have a molecular formula (C ₅H ₈) _nHydrocarbon, wherein n is preferably 2 to about 6, and even more preferably 2 to 4.Has formula C according to the present invention ₁₀H ₁₆The terpenes of (comprising the form of being substituted) is sometimes referred to as monoterpene in this article, and has formula C ₁₅H ₂₄The terpenes of (comprising the form of being substituted) is sometimes referred to as sesquiterpene in this article.Has formula C according to the present invention ₂₀H ₃₂The terpenes of (comprising the form of being substituted) is sometimes referred to as two terpenes in this article, and has formula C ₃₀H ₂₄The terpenes of (comprising the form of being substituted) is sometimes referred to as triterpene in this article, etc.The terpenes that contains 30 or 30 above carbon is merged and forms with regular pattern by two terpenes precursors usually.Though expect that all such terpenes all are applicable to the present invention, the first-selected usually monoterpene that uses.

In some preferred embodiment, the terpene compound of the present composition preferably comprises one or more acyclic terpenes compounds of exhausted vast scale, and even more preferably is made up of one or more acyclic terpenes compounds basically.In acyclic terpenes, expect that described compound all may belong to the compounds category of confirming as the isoprenoid that is end-to-end or be not among the compounds category that engages in this way.The acyclic terpenes that is preferred in some aspect of the present invention comprises myrcene (2-methyl-6-methylene radical suffering-1,7-diene), alloocimene, β-ocimene.

In certain embodiments, terpene compound of the present invention can comprise the ring-type terpene compound.In the ring-type terpenes, monocycle, dicyclo, three rings or tetracyclic compound that expection has different degrees of unsaturation can be used for the present invention.

The example that is suitable for the terpene compound that uses in conjunction with all respects of the present invention comprises terebene (terebene), myrcene, limonene (limonene), retinene (retinal), firpene (pinene), menthol (menthol), Geraniol, farnesol, phytol (phytol), vitamin A ₁, terpinene (terpinene), δ-3 carene (delta-3carene), terpinolene (terpinolene), phellandrene (phellandrene), fenchene (fenchene) etc. with and blend, comprise all isomer.

The example of terpene derivatives of the present invention comprises terpenic containing oxygen derivative, for example contains alcohols, aldehydes or the ketone of hydroxyl or carbonyl, and hydrogenated derivatives.Terpenic containing oxygen derivative is sometimes referred to as terpenoid in this article.In certain embodiments, dialkylene compound of the present invention comprises terpenoid Salvin (Carnosic acid).Salvin is a kind of phenols two terpenes corresponding to empirical formula C2028O4.Its natural resulting from Labiatae (Libiatae) plant.For example, Salvin be Salvia japonica Thunb. (Salvia officinalis, sage) and Rosmarinus officinalis (Rosmarinus officinalis, rosemary) composition of species mainly is found in the blade.In Thymus vulgaris (thyme) and marjoram (marjoram) (referring to the Salvia officinalis[Helv.Chim Acta 47 of Linde, 1234 (1962)] and the Rosmarinusofficinalis[J.Org.Chem.30 of Wenkert, 2931 (1965)]) and in various other Salvia japonica Thunb. species (referring to Salviacanadensis[Savona and Bruno, J.Nat.Prod.46,594 (1983)] and people such as Salvia willeana[de la Torre, Phytochemistry 29,668 (1990)]) also found Salvin.It also is present in threeleaf sage root (Salviatriloba) and the Clary Sage (Salvia sclarea).Other possible terpenoid is described as follows:

C. other component

Composition of the present invention may be optionally in conjunction with other component, and this depends on special desired use and used concrete iodine hydrocarbon and dialkylene compound.

Other stablizer of 1-

For instance, composition of the present invention may comprise other stablizer in addition, the for example combination of (but being not limited to) phenols, epoxides, phosphorous acid esters and phosphoric acid ester and described each thing, in the U.S. patent application case 11/109,575 in the application that coexists of on April 18th, 2005 application (incorporating this paper by reference into) these materials are disclosed.In certain embodiments, aromatic epoxide in the first-selected epoxides and fluoro-alkyl epoxide are as the additional stability agent.

Expect that any phenolic compound all is suitable as the optional stablizer in the present composition.Though the applicant does not wish to be subjected to any theory of operation to fetter, but still think that phenols of the present invention serves as free-radical scavengers in the present composition, and therefore tend to increase the stability of described composition.Term " phenolic compound " typically refers to any phenol that is substituted or is unsubstituted as used herein.The example of suitable phenolic compound comprises 4,4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 4,4 '-two (2, the 6-DI-tert-butylphenol compounds), 2,2-or 4, the 4-'-biphenyl diphenol (comprises 4,4 '-two (2-methyl-6-tert butyl phenol), 2,2-or 4, the derivative of 4-'-biphenyl diphenol, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 4,4,-butylidene-bis(3-methyl-6-t-butyl phenol), 4,4,-isopropylidene two (2, the 6-DI-tert-butylphenol compounds), 2,2 '-methylene-bis(4-methyl-6-nonyl phenol), 2,2 '-isobutylidene two (4, the 6-xylenol), 2,2,6-di-tert-butyl-4-methy phenol (BHT), 2,6-di-t-butyl-4-ethylphenol, 2,4 dimethyl 6 tert butyl phenol, 2,6-two-uncle-alpha, alpha-dimethyl amino-p-cresol, 2,6-di-t-butyl-4 (N, N '-dimethylaminomethylphenol), 4,4 '-thiobis (2-methyl-6-tert butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert butyl phenol), two (3-methyl-4-hydroxyl-5-tert.-butylbenzene methyl) thioether and two (3,5-di-t-butyl-4-hydroxybenzene methyl) thioethers etc.Other suitable phenols comprises other derivative of tocopherol, quinhydrones, tertiary butylated hydroquinone and quinhydrones etc.Some preferred phenols comprises tocopherol, BHT, quinhydrones etc.Some especially preferred phenols comprises tocopherol etc.Most of phenols can be buied, for example available from the Irganox compound of Ciba.Can use the mixture of single phenolic compound and/or two or more phenols in the composition of the present invention.

Expect that also any epoxide all is suitable in the composition of the present invention.Though the applicant does not wish to be subjected to any theory of operation to fetter, but still think that epoxide of the present invention is at CF ₃Serve as acid scavenger in the I composition, and therefore tend to increase the stability of described composition.The example of suitable aromatic epoxide comprises the epoxide by the following formula I definition:

Wherein: R be hydrogen, alkyl, fluoroalkyl, aryl, fluoro aryl or

And

Ar is phenylene or the naphthylidene part that is substituted or is unsubstituted.Some preferred formula I aromatic epoxide comprises: butylphenyl glycidyl ether, the amyl group phenyl glycidyl ether, the hexyl phenyl glycidyl ether, the heptyl phenyl glycidyl ether, the octyl phenyl glycidyl ether, the nonyl phenyl glycidyl ether, the decyl phenyl glycidyl ether, the glycidyl methyl phenyl ether, 1,4-diglycidyl phenyl diether and derivative thereof, 1,4-diglycidyl naphthyl diether and derivative and 2,2 ' [[[5-17 fluorine octyl groups] 1, the 3-phenylene] two [[2,2, the 2-trifluoromethyl] ethylidene] the oxygen methylene] bisoxirane etc.Other preferred aromatic epoxide comprises the derivative of naphthyl glycidyl ether, 4-methoxyphenyl glycidyl ether and naphthyl glycidyl ether etc.Some more preferred aromatic epoxide comprises butylphenyl glycidyl ether etc.Can use the mixture of single aromatic epoxide and/or two or more aromatic epoxide in the composition of the present invention.

Any alkyl and/or alkenyl epoxides all are suitable in the composition of the present invention.The example of suitable alkyl and alkenyl epoxides comprises formula II epoxide:

R wherein _AlkBe the alkyl or alkenyl that is substituted or is unsubstituted.Preferably, R _AlkFor having about 1, more preferably has about 1 the alkyl or alkenyl that is substituted or is unsubstituted to about 6 carbon atoms to about 10 carbon atoms.Some preferred formula II alkyl epoxide comprises n-butyl glycidyl ether, isobutyl-glycidyl ether, hexanediol diglycidyl ether etc. and fluoro and perfluoroalkyl epoxide.Preferred alkyl epoxide comprises hexanediol diglycidyl ether.Some preferred formula II alkenyl epoxides comprises glycidyl allyl ether, fluoro and perfluor epoxide etc.Preferred alkenyl epoxides comprises glycidyl allyl ether etc.

According to some preferred embodiment, composition of the present invention comprises at least a dialkylene compound (isoprene for example, propadiene and myrcene) and a kind of additional stability combination of compounds, described stable compound is selected from: epoxides (for example aromatic epoxide and fluoro-alkyl epoxide), Hinered phenols (for example the DL-alpha-tocopherol and the 2-tertiary butyl-4, the 6-xylenol), phosphorous acid esters (for example separately and diphenyl phosphate (for example Doverphos 213) and triphenyl phosphite, for example the Doverphos 9EII of form of mixtures), the mixture of the ester class of phosphorous acid (for example Doverphos 613) and these materials.

Can use at least a dialkylene compound and the additional optional stabilizer compounds of any suitable relative quantity.For example, in some preferred embodiment, the weight ratio of dialkylene compound and other stabilizer compounds arrived in about 100: 0 scope at about 1: 99.In preferred embodiment, the weight ratio of dialkylene compound and optional stablizer is about 10: 1 to about 1: 1, more preferably about 2: 1 to about 1: 1, and even more preferably about 1: 1.

2-auxiliary refrigerant, auxiliary blowing agent etc.

According to some embodiment, as explaining more comprehensively that hereinafter composition of the present invention also can comprise the desired use of looking composition and one or more components that exist in addition except iodine hydrocarbon and stablizer.For example, composition of the present invention is fit to use in conjunction with following should being used for usually, and various auxiliary components can be used for following with described composition associating and other is used: conducting heat (comprises that refrigeration, refrigerator are used, closed rankine cycle (closed Rankine cycle, CRC) operation; Organic Rankine cycle operation (ORC); Foam and/or foam shaping operation (comprise as complete Preblend or a part and/or whipping agent and/or foam (comprising thermoset foam (for example urethane, poly-isocyanurate and phenol are thing), thermoplastic expanded body (for example polystyrene and polyolefine), whole skin foam, one or both component pressurization bubble foaies (pressurized froth foam) etc.); Solvent (comprising solvent cleaning and extraction); Aerosol; Oligopolymer and/or polymer production (monomer that for example is used for polyreaction); Propelling agent; The fire extinguishing auxiliary agent; Tensio-active agent; Flush applications; Quantitative inhalation (MDI); Lubricant; Fire inhibitor; Therapeutic composition; Insecticides; Herbicidal composition; Solvent application (comprising cleaning, extraction and deposition applications) etc.

Though expect that many auxiliary components can be advantageously used in the composition of the present invention, preferably, composition of the present invention contains one or more components in following as auxiliary component in several embodiment:

CO ₂；

Hydro carbons (being substituted and being unsubstituted, especially is the C2-C6 hydrocarbon);

Alcohols (being substituted and being unsubstituted, especially is C2-C6 alcohol);

Ketone (being substituted and being unsubstituted, especially is C2-C5 ketone);

Aldehydes (being substituted and being unsubstituted, especially is C2-C5 aldehyde);

Ethers/two ethers (being substituted and being unsubstituted, especially is C2-C5 ether);

Fluorine ethers (being substituted and being unsubstituted, especially is C2-C5 fluorine ether);

Fluoroolefin class (being substituted and being unsubstituted, especially is the C2-C6 fluoroolefin);

CFC (especially being C2-C5CFC);

HFC (especially being C2-C5HFC);

HCC (especially being C2-C5HCC);

HCFC (especially being C2-C5HCFC);

The haloalkene hydro carbons preferably includes fluoroolefin class (being substituted and being unsubstituted, especially is the C2-C6 fluoroolefin);

HFO (especially being C2-C5HFO);

HClFO (especially being C2-C5HClFO);

HBrFO (especially being C2-C5HBrFO);

Carbonates/two carbonates;

Carboxylic-acid and derivative thereof (for example carboxylicesters, for example methyl-formiate); And water.

The compound of other atom is formed and do not had to term " HFO " expression by carbon, fluorine and hydrogen atom as used herein, and wherein have at least one carbon-to-carbon double bond.

The compound of other atom is formed and do not had to term " HClFO " expression by carbon, chlorine, fluorine and hydrogen atom as used herein, and wherein have at least one carbon-to-carbon double bond.

The compound of other atom is formed and do not had to term " HBrFO " expression by carbon, bromine, fluorine and hydrogen atom as used herein, and wherein have at least one carbon-to-carbon double bond.

Be meant compound with at least one carbon atom and at the most about five carbon atoms as title C1-C5 used in specification sheets and claims and similar term in the whole text, etc.

Though expect that multiple HFC can be used in the compositions and methods of the invention, in some preferred embodiment, preferably in composition, use one or more compounds (comprising separately any isomer and all isomer) in following:

Methylene fluoride (HFC-32);

Pentafluoride ethane (HFC-125);

1,1,2,2-Tetrafluoroethane (HFC-134);

1,1,1,2-Tetrafluoroethane (HFC-134a);

Halothane (HFC-143a);

C2H4F2 C2H4F2 (HFC-152a);

1,1,1,2,3,3,3-heptafluoro-propane (HFC-227ea);

1,1,1,3,3,3-HFC-236fa (HFC-236fa);

1,1,1,3,3-pentafluoropropane (HFC-245fa); With

1,1,1,3,3-3-pentafluorobutane (HFC-365mfc).

Though expect that multiple HCFC can be used in the compositions and methods of the invention, but in some preferred embodiment, preferably use separately or in any combination following each thing: dichlorotrifluoroethane (for example 2,2-two chloro-1,1,1-Halothane (HCFC-123)) and chloro-tetrafluoroethane (HCFC-124), comprise separately any isomer and all isomer.

Though expect that multiple HCC can be used in the compositions and methods of the invention, but in some preferred embodiment, preferably use separately or in any combination following each thing: Ethylene Dichloride (for example 1, the 2-ethylene dichloride, comprise anti--1,2-dichloroethene), monochloroethane and 2 cbloropropane isopropyl chloride.

Though expect that multiple CFC can be used in the compositions and methods of the invention, in some preferred embodiment, preferably use Refrigerant R 113 (for example 1,1,2-Refrigerant R 113 (CFC-113)), especially as the monomer of producing oligopolymer and/or polymkeric substance.

Though expect that multiple fluoroolefin can be used in the compositions and methods of the invention, especially preferred in many examples is that described composition comprises one or more C3 or C4 fluoroolefin, the formula I compound shown in being preferably as follows:

XCF _zR _3-z(I)，

Wherein X is C ₂Or C ₃Unsaturated, as to be substituted or to be unsubstituted alkyl, each R are Cl, F, Br, I or H independently, and z is 1 to 3.Particularly preferably be following compounds in the formula I compound:

Vinyl fluoride;

The fluorine propylene;

The fluorine butylene;

The chlorine vinyl fluoride;

Chlorine fluorine propylene; With

Chlorine fluorine butylene.

Be preferred among the vinyl fluoride in the certain embodiments of the invention be: C ₂H ₃F (single vinyl fluoride or vinyl fluoride or VF); C ₂H ₂F ₂(vinylidene fluoride (vinylidene fluoride or VDF) for example; C ₂HF ₃(trifluoro-ethylene or THFE) and C ₂F ₄(tetrafluoroethylene or TFE).

Be preferred among the fluorine propylene in the certain embodiments of the invention be: C ₃H ₃F ₃(comprise all isomer, for example 3,3,3-trifluoro propene (HFO-1243zf); C ₃H ₂F ₄(for example 1,3,3,3-tetrafluoeopropene (HFO-1234ze) and 2,3,3, the cis-trans-isomer of 3-tetrafluoeopropene (HFO-1234yf)) and C ₃HF ₅(for example isomer of HFO-1225).

Term used herein " HFO-1234 " is meant all tetrafluoeopropenes.Described tetrafluoeopropene comprises HFO-1234yf and its any He all steric isomers or geometrical isomer.Term HFO-1234yf used herein and HFO-1234ze generally are meant 1,1,1 respectively, 2-tetrafluoeopropene and 1,1,1, the 3-tetrafluoeopropene, and no matter its three-dimensional isomery how.

The HFO-1234 compound is a kind of known substance, is listed in " chemical abstracts " database.United States Patent (USP) the 2nd, 889, No. 379, the 4th, 798, No. 818 and the 4th, 465, in No. 786 (all incorporating this paper by reference into) described through various saturated and unsaturated halogen-containing C ₃The gas phase catalytic fluorination reaction of compound produces as CF ₃CH=CH ₂The method of fluorine propylene.EP 974,571 (incorporating this paper by reference into) also discloses by making 1,1,1,3,3-pentafluoropropane (HFC-245fa) in gas phase, at high temperature contact with chromium-based catalysts or in liquid phase with KOH, NaOH, Ca (OH) ₂Or Mg (OH) ₂Alcoholic solution contact and prepare 1,1,1, the method for 3-tetrafluoeopropene.

Be preferred among the fluorine butylene in the certain embodiments of the invention be: C ₄H ₄F ₄(comprising its all isomer); C ₄H ₃F ₅(for example all isomer of HFO-1345) and C ₄H ₂F ₆(for example all isomer of HFO-1336).

Be preferred among the chlorine vinyl fluoride in the certain embodiments of the invention be: C ₂F ₃Cl (CTFE).

Be preferred among the chlorine fluorine propylene in the certain embodiments of the invention be: monochloro generation or compound of dichloro for example comprise: C ₃H ₂F ₄(for example the 2-chloro-3,3,3-three fluoro-1-propylene (comprising HCFO-1233xf) and 1-chloro-3,3,3-three fluoro-1-propylene (all isomer that comprise HCFO-1233zd) for Cl.

In some preferred embodiment of the present invention, described composition comprises at least a formula II fluoroolefin:

Wherein each R is Cl, F, Br, I or H independently,

R ' is (CR ₂) _nY,

Y is CRF ₂,

And n is 0 or 1.

In particularly preferred embodiment, Y is CF ₃, n be 0 and residue at least one R among the R be F.

The applicant thinks, generally be effective when above formula I of Que Rening and II compound are in being included in the present composition, and in all purposes of above confirming, all show effectiveness, especially be included in the purposes in refrigerant composition of the present invention, foaming agent composotion, compatilizer, aerosol, propelling agent, spices, perfume formulation and the solvent compositions.Yet the applicant is surprised and be surprised to find that, some compound with above-mentioned chemical formula structure is compared with described other compound and shown quite favourable low toxicity levels.Can recognize easily that this finds not only for the preparation of refrigerant composition but also for the preparation of any and all compositions all very advantageous and benefit, otherwise described composition will contain the relative toxicity compound that satisfies above-mentioned chemical formula.More particularly, the applicant thinks that (preferably wherein Y is CF to formula II compound ₃) produce low relatively toxic level, wherein at least one R on the unsaturated ends carbon is H, and at least one R among the residue R is F.The applicant thinks that also all constitutional isomers, geometrical isomer and the steric isomer of described compound all are effectively and have favourable hypotoxicity.

In particularly preferred embodiment, especially in comprising the embodiment of above-mentioned low toxicity compounds, n is 0.In some particularly preferred embodiment, composition of the present invention comprises one or more tetrafluoeopropenes.Term used herein " HFO-1234 " is meant all tetrafluoeopropenes.Preferred especially HFO-1234yf uses in conjunction with heat transfer compositions, method and system among the tetrafluoeopropene.

In other embodiments, can preferably use suitable-or/and anti--1,3,3,3-tetrafluoeopropene (HFO-1234ze).Term HFO-1234ze used herein generally is meant 1,3,3, the 3-tetrafluoeopropene, and no matter be cis or trans.Term used herein " along HFO-1234ze " and " anti-HFO-1234ze " describe 1,3,3 respectively, the cis of 3-tetrafluoeopropene and trans.Therefore, the scope of term " HFO-1234ze " comprises all combinations and the mixture along HFO-1234ze, anti-HFO-1234ze and described material.

Though the character along HFO-1234ze and anti-HFO-1234ze is different at least in some aspects, expect that these compounds are suitable for using in conjunction with various application as herein described, method and system separately or with other compound that comprises its steric isomer separately.For instance, though anti-HFO-1234ze is preferred in some refrigeration system because of low relatively boiling point (19 ℃), but still the expection boiling point also has effectiveness for+9 ℃ suitable HFO-1234ze in some refrigeration system of the present invention.Therefore, should be appreciated that term " HFO-1234ze " and 1,3,3,3-tetrafluoeopropene are meant two kinds of steric isomers, unless and other regulation, otherwise use this term to be intended to show cis and transly be applicable to separately and/or can be used for specifying purpose.

The HFO-1234 compound is a known substance, is listed in " chemical abstracts " database.United States Patent (USP) the 2nd, 889, No. 379, the 4th, 798, No. 818 and the 4th, 465, No. 786 (incorporating this paper by reference into) described through various saturated and unsaturated halogen-containing C ₃The gas phase catalytic fluorination reaction of compound produces as CF ₃CH=CH ₂The method of fluorine propylene.EP974 also disclosed by making 1,1,1,3 571 (incorporating this paper by reference into), 3-pentafluoropropane (HFC-245fa) in gas phase, at high temperature contact with chromium-based catalysts or in liquid phase with KOH, NaOH, Ca (OH) ₂Or Mg (OH) ₂Alcoholic solution contact and prepare 1,1,1, the method for 3-tetrafluoeopropene.In addition, for example, the method of producing The compounds of this invention has been described in conjunction with the U.S. patent application case 10/694,272 " Process for Producing Fluoropropenes " in the application and in the U.S. Provisional Application case 60/733355 (incorporating this paper separately by reference into) of application on November 3rd, 2005.

It is believed that, composition of the present invention, the composition that especially comprises HFO-1234 and HFO-1234yf has the favorable properties for multiple major reason.For instance, to small part based on mathematical modeling, the applicant thinks that fluoroolefin of the present invention does not have substantial negative impact to atmospheric chemistry, compares the ozone depletion that is caused with other some halogenated materials and can ignore.Therefore, preferred composition of the present invention has the advantage that does not cause ozone depletion substantially.Preferred composition is compared with many hydro fluoroalkaness of present use and is not also caused Global warming substantially.

The visual special applications of content of present composition Chinese style I compound (especially being HFO-1234) and extensively changing, and the content of described compound all belongs within the broad range of the present invention greater than about 1 weight % and less than the composition of 100 weight %.In a preferred embodiment, composition of the present invention comprise about 5 weight % to about 99 weight % and even more preferably about 5 weight % to the HFO-1234 of about 95 weight %, be preferably HFO-1234yf.

For example, rather than must be limited, in some preferred embodiment of the present composition except iodine hydrocarbon compound of the present invention (and except stabilizer compounds (when existing)), can also comprise fluoroolefin compound of the present invention and/or HFC extensive, middle and more specifically range of compositions interior (all amounts all are interpreted as usefulness " pact " modification) as shown in the table, wherein per-cent is the gross weight meter of three kinds of components shown in the according to the form below 1.

Table 1

	The wt% broad range	The wt% intermediate range	The concrete scope of wt%
				Fluoroolefin	0-95	5-85	5-80 or 0
The iodine hydrocarbon	＞0-99	10-90	15-90 or 60-80
				HFC	0-95	5-85	5-80 or 20-40

Except the stablizer and the also preferred any oil or lubricant that exists that in heat-transfer fluid, preferably exist according to the present invention, can also comprise CF in some preferred embodiment of the present composition ₃I and one or more fluoroolefin compounds.In some preferred form, fluoroolefin is made up of tetrafluoeopropene basically, more preferably is made up of HFO-1234yf.Extensively, middle and more specifically range of compositions (all amounts all are interpreted as usefulness " pact " modification) is as shown in the table, wherein per-cent is the summation meter of component shown in the following table 2.

Table 2

	The wt% broad range	The wt% intermediate range	The concrete scope of wt%
				Fluoroolefin (being preferably HFO-1234yf)	10-95	50-90	60-80
CF 3I	＞0-＜90	10-50	20-40

Some special preferred embodiment of the present invention comprises heat-transfer fluid, is particularly useful in the automotive air-conditioning system, and it is about 65% to about 75% HFO-1234yf and about 25% to about 35% CF that described heat-transfer fluid comprises weight percent ₃I, and even more preferably to comprise weight percent be about 70% HFO-1234yf and about 30% CF ₃I, described per-cent are with HFO and CF ₃The gross weight meter of I.

In some preferred embodiment of the present composition except any stablizer that exists according to the present invention, can also comprise as shown in the table extensively, the middle and CF of (all amounts all are interpreted as usefulness " pact " modification) in the range of compositions more specifically ₃I, some fluoroolefin compound (being preferably HFO-1234ze) of the present invention and/or some HFC (being preferably HFC-152a), wherein per-cent is the summation meter with three kinds of components shown in the table 3.

Table 3

	The wt% broad range	The wt% intermediate range	The concrete scope of wt%
				Fluoroolefin (being preferably HFO-1234ze)	0-85	0-85	0
CF 3I	＞0-＜100	10-＜100	60-80
				HFC (being preferably HFC-152a)	0-95	25-90	20-40

In some preferred embodiment of the present composition except stablizer of the present invention, can also comprise as shown in the table extensively, the middle and CF of (all amounts all are interpreted as usefulness " pact " modification) in the range of compositions more specifically ₃I, some fluoroolefin compound of the present invention and/or some HFC (being preferably HFC-32), wherein per-cent is the summation meter with three kinds of components shown in the table 4.

Table 4

	The wt% broad range	The wt% intermediate range	The concrete scope of wt%
				Fluoroolefin	0-75	0-75	0-75
CF 3I	＞0-40	＞1-33	＞1-15
				HFC (being preferably HFC-32)	50-＜100	65-＜95	85-99

The 3-lubricant

According to some aspect of the present invention, except the iodine hydrocarbon compound, also comprise lubricant or oil in the described composition.Any traditional lubrication agent may be used in the composition of the present invention.As hereinafter explaining more comprehensively, described composition especially is suitable as the refrigeration agent in heating or the cooling-cycle apparatus.

Other component of 4-

Can use any other additive in the composition of the present invention.The example of appropriate addn comprises metal passivator (for example Nitromethane 99Min.), the oilness of improving lubricant and extreme pressure (EP) additive of load-bearing feature.The example of EP additive is at United States Patent (USP) the 4th, 755, describes to some extent in No. 316 (table D) and incorporates into herein.The example of EP additive is an organophosphorus compounds, comprises the Lubrizol  8478 that is made by Lubrizol Corporation.Can also use among the 4th, 755, No. 316 tables of corrosion inhibitor and United States Patent (USP) D and also disclose these corrosion inhibitors.

II. heat transfer compositions

Though expect that composition of the present invention can comprise all cpds mentioned in this article of broad range amount, but generally preferably, heat transfer compositions of the present invention and especially refrigerant composition comprise the weight percent that accounts for composition and are at least about 25% iodine hydrocarbon compound, and even more preferably C1-C3 iodine fluorocarbon compound.Comprise HFC and especially comprise in some preferred embodiment of HFC-152a at composition, composition comprises weight percent content and is at least about 40% and even more preferably at least about 50% HFC-152a.

Preferred refrigerant of the present invention or heat transfer compositions are particularly useful for the refrigeration agent or the heat transfer compositions of vapor compression system, comprise that the weight percent that accounts for composition is about 30% to about 50% lubricant.An important requirement to lubricant is the compressor of the lubricant retrieval system of capacity to be arranged so that make compressor lubrication.Therefore, the suitability of lubricant part is by the refrigerant/lubricant characteristics determined, and part is determined by system features.The example of proper lubrication agent comprises mineral oil, alkylbenzene, polyol ester (comprising polyalkylene glycol), polyvinyl ether (PVE) etc.Commercially available have mineral oil, comprises paraffin oil or naphthenic oil.Commercially available mineral oil comprises the Sunisco 3GS of Zerol300 (registered trademark), Witco of Witco LP 250 (registered trademark), Shrieve Chemical of Witco and the Calumet R015 of Calumet.Commercially available alkyl benzene lubricants comprises Zerol 150 (registered trademark).Commercially available ester comprises two n-nonanoic acid DOPCP (neopentyl glycoldipelargonate), can Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark) buy.Other ester that is suitable for comprises phosphoric acid ester, diester and fluorine ester.In some cases, alkyl oil has enough solvabilities to the refrigeration agent that comprises the iodine hydrocarbon, and the combination of iodine hydrocarbon and hydrocarbon ils may be more more stable than the lubricant of other type.Therefore, described combination may be favourable.Preferred lubricant comprises polyalkylene glycol and ester.Particularly preferably be polyalkylene glycol in certain embodiments, because they are used at present as special applications such as automative air conditionings.Certainly, also can use the different mixtures of dissimilar lubricants.

Be the consistency and/or the solvability of auxiliary lubricant, the preferred form of the present composition also can comprise compatilizer, for example propane.The weight percent content of described compatilizer (comprising propane, butane and pentane) in composition is preferably about 0.5% to about 5%.As United States Patent (USP) the 6th, 516, No. 837 (incorporating this paper by reference into) are disclosed, also the combination of tensio-active agent and solubilizing agent can be added in the composition of the present invention with auxiliary oily solvability.

Many existing refrigeration systems are suitable for using in conjunction with existing refrigeration agent at present, and it is believed that some composition of the present invention has been adapted at or has not had being used for many these type systematics under the improved situation of system.In many application, composition of the present invention can provide as present advantage based on the substitute in the system with relative heavy body refrigeration agent.In addition, for example for cost consideration, use at needs of the present inventionly to substitute among the embodiment of higher capacity refrigeration agent than the lower volume refrigerant composition, the described embodiment of the present composition can provide potential advantages.Therefore, preferably use composition of the present invention in certain embodiments, especially the composition that comprises the anti-HFO-1234yf of suitable vast scale, and comprise the substitute of the composition of the anti-HFO-1234yf of exhausted vast scale in certain embodiments as existing refrigeration agent (for example HFC-134a).In some applications, refrigeration agent of the present invention may allow advantageously to use big capacity compressors, thereby produces the energy efficiency that is better than other refrigeration agent (for example HFC-134a).Therefore, refrigerant composition of the present invention, the composition that especially comprises anti-HFP-1234ze provides the possibility that realizes competitive advantage on energy foundation for the refrigeration agent alternate application.

Expect composition of the present invention, especially comprise that those contain the composition of HFO-1234 (and especially for HFO-1234yf), also have advantage (in original system maybe when being used as the substitute of refrigeration agents such as R-12 and R-500) usually with in the refrigerator that the business air conditioner system is used in combination.According to the present invention, in described some embodiment, comprise in HFO-1234 composition of the present invention that preferably about 0.5 weight % arrives about 60 weight %, more preferably from about 20 weight % are preferably the iodine hydrocarbon, for example CF to the fire inhibitor of about 50 weight % ₃I.

Therefore, method of the present invention, system and composition are suitable for waiting and using in conjunction with automotive air-conditioning system and device, business-use refrigrating system and device, refrigerator, resident's refrigerator and reach in freezer, general air conditioning system, heat pump, ORC, CRC.

III. whipping agent, foam and foaming composition

Whipping agent also can comprise one or more compositions of the present invention or be made of one or more compositions of the present invention.As indicated above, composition of the present invention can comprise the iodine hydrocarbon compound of the present invention and the dialkylene compound of broad range amount.But for for the preferred composition of whipping agent of the present invention, the general preferably weight percent content of iodine hydrocarbon compound in composition is at least about 1%, and even more preferably at least about 50%.

In some preferred embodiment, except HFO-1234 (being preferably HFO-1234ze), also comprise a kind of or a kind of component in following in the foaming agent composotion of the present invention as auxiliary blowing agent, filler, vapour pressure conditioning agent, or be used for other any purpose:

Methylene fluoride (HFC-32);

Pentafluoride ethane (HFC-125);

1,1,2,2-Tetrafluoroethane (HFC-134);

1,1,1,2-Tetrafluoroethane (HFC-134a);

C2H4F2 C2H4F2 (HFC-152a);

1,1,1,2,3,3,3-heptafluoro-propane (HFC-227ea);

1,1,1,3,3,3-HFC-236fa (HFC-236fa);

1,1,1,3,3-pentafluoropropane (HFC-245fa);

1,1,1,3,3-3-pentafluorobutane (HFC-365mfc);

Water;

CO ₂；

Methyl-formiate and derivative thereof;

Alcohols (C1-C4) and derivative thereof;

Ketone and derivative thereof;

Aldehydes and derivative thereof;

Ethers/two ethers and derivative thereof;

Carbonates and derivative thereof;

Two carbonates and derivative thereof;

With carboxylic-acid and derivative thereof.

Expect that foaming agent composotion of the present invention can comprise along HFO-1234ze, anti-HFO1234ze or its combination.In some preferred embodiment, foaming agent composotion of the present invention comprises suitable: anti-weight ratio is about 1: 99 to about 30: 70, and even more preferably about 1: 99 to about 5: 95 suitable HFO-1234ze and the combination of anti-HFO1234ze.

In other embodiments, the invention provides foaming composition, and one or both components pressurization bubble foaies of optimization polyurethane, poly-isocyanurate, phenols foam, extrusion of thermoplastic foamed body composition, whole skin foam and the preparation of the use present composition.In described foam embodiment, one or more compositions in the present composition are included in the foaming composition fully or as the part of whipping agent, know as affiliated field, described composition preferably includes one or more and can react under proper condition and/or bubble to form the annexing ingredient of foam or polynuclear plane.The present invention also relates to by the prepared foam of polymer foaming body prescription that contains the whipping agent that comprises the present composition, and be preferably the obturator-type foam.In other embodiments, the invention provides the foaming composition that comprises thermoplastic expanded body, for example polystyrene (PS), polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) foam are preferably low-density foamed body.

In some preferred embodiment, also dispersion agent, foaming stabilizer, tensio-active agent and other additive can be incorporated in the foaming agent composotion of the present invention.According to circumstances, but preferably add tensio-active agent and serve as foaming stabilizer.Some representative substances are sold with the title of DC-193, B-8404 and L-5340, be generally for example United States Patent (USP) the 2nd, 834, No. 748, the 2nd, 917, No. 480 and the 2nd, 846, No. 458 disclosed silicone polyethers (polysiloxane polyoxyalkylene) segmented copolymer, described patent is incorporated herein by reference separately.The optional additive of other of blowing agent blends can comprise fire retardant, for example tricresyl phosphate (2-chloroethyl) ester, tricresyl phosphate (2-chloropropyl) ester, tricresyl phosphate (2, the 3-dibromopropyl) ester, tricresyl phosphate (1,3-two chloropropyls) ester, diammonium phosphate, various halogenated aromatic compound, weisspiessglanz, aluminum trihydrate, polyvinyl chloride etc.

IV. propellant compositions

On the other hand, the invention provides the propellant compositions that comprises composition of the present invention or be made up of composition of the present invention basically, described propellant compositions is preferably jettable compositions.The propelling agent that propellant compositions of the present invention preferably comprises material to be sprayed and comprises composition of the present invention, is made up of composition of the present invention or is made up of composition of the present invention basically.But also can there be inert fraction, solvent and other material in the spray mixture.Preferably, jettable compositions is an aerosol.Suitable substance to be sprayed includes, but is not limited to cosmetic substance, for example reodorant, perfume, hair jelly, sanitising agent and rumbling compound and medicinal substance, for example anti-asthma and halitosis medicine and any other medicine etc. preferably include any other medicine or medicament to be sucked.The medicine or other therapeutical agent that preferably have therapeutic dose in the composition, in the composition quite the rest part of vast scale comprise formula I compound of the present invention, be preferably HFO-1234, and even HFO-1234ze more preferably.

Industry, user or the aerosol products that pharmaceutically uses contain one or more propelling agents and one or more activeconstituentss, inert fraction or solvent usually.Propelling agent provides the power with atomised form ejection product.Though some aerosol products are by compressing gas propulsive as carbonic acid gas, nitrogen, nitrous oxide even air etc., most of commercial aerosol use liquefied gas propellant.The most frequently used liquefied gas propellant is a hydro carbons, for example butane, Trimethylmethane and propane.Also use dme and HFC-152a (1, the 1-C2H4F2 C2H4F2) separately or with the hydrocarbon propellant blend.Unfortunately, these liquefied gas propellant all are highly combustible, and it are incorporated into regular meeting produces flammable aerosol products in the aerosol formulations.

The applicant has begun to recognize the non-inflammability liquefied gas propellant that still needs to be used for preparing aerosol products.The invention provides composition of the present invention, especially and be preferably and comprise HFO-1234, and even more preferably comprise the composition of the combination of HFO-1234ze and/or HFO-1234yf, be used for some industrial aerosol products (for example comprising spray cleaner, lubricant etc.) and medicinal aerosol formulations (for example comprising the aerosol that transmits medicine to lung or mucous membrane).Example comprises and is used for the treatment of asthma and other chronic obstructive pulmonary disease and is used for to accessibility mucous membrane or by transmitting the quantitative inhalation (MDI) of medicine in the nose.Therefore, the present invention includes the method for the illness, disease and the similar health problem that are used for the treatment of organism (for example mankind or animal), comprise to the organism of needs treatment and use the present composition that contains medicine or other therapeutic component.In some preferred embodiment, the step of using the present composition comprises provides the MDI that contains the present composition (for example, composition being introduced among the MDI), and then discharges composition of the present invention from MDI.

Composition of the present invention, the composition that especially comprises or mainly comprise HFO-1234 (being preferably HFO-1234ze and/or HFO-1234yf) can provide non-inflammability liquefied gas propellant and the aerosol that does not cause Global warming substantially.Composition of the present invention can be used for preparing the aerosol (for example personal care product, household product and automobile product) that various industrial aerosols or other jettable compositions (for example contact sanitising agent (contact cleaner), fly-ash separator, lubricant spraying etc.) and user use.HFO-1234ze especially is preferably used as the main ingredient of the propellant compositions in the medicinal aerosol formulations (for example quantitative inhalation).Medicinal aerosol formulations of the present invention and/or propelling agent and/or jettable compositions in many application except formula (I) or (II) the compound (preferred HFO-1234ze), also comprise for example medicine of beta-2-agonists, reflunomide or other medicine, and also comprise other composition according to circumstances, for example tensio-active agent, solvent, other propelling agent, essence and other vehicle.Different with many compositions in the past used in the described application, composition of the present invention has good environmental characteristics, and is considered to can not cause Global warming.Therefore, composition of the present invention provides the low-down non-inflammability substantially of global warming potential liquefied gas propellant in some preferred embodiment.

V. essence and spices

Composition of the present invention is in a part that is used as perfume formulation and fragrance formulations and especially also have advantage aspect the supporting agent of perfume formulation and fragrance formulations.Prove that by the testing sequence of 0.39 gram jasmone (Jasmone) being put into heavy-walled glass tubes the present composition is used for the suitability of described purpose.1.73 gram R-1234ze are added in the glass test tube.Then freezing and sealing with test tube.When thawing test tube, find that mixture has a liquid phase.It is 20% jasmone and 80% R-1234ze that solution contains weight percent, thereby can be advantageously used for the supporting agent or the part of perfume formulation transfer system in aerosol and other prescription.Also make it may be as spices extraction agent (comprising) from plant extract.In certain embodiments, may preferably in extracting application, use composition of the present invention and the fluid of the present invention that is in supercritical state.Relate to and use overcritical or use and other is applied in hereinafter and is described near this of the present composition of supercritical state.

VI. stabiliser composition

On the one hand, the invention provides the stabiliser composition that in above-mentioned arbitrary composition, is used as additive, or more generally as any stabiliser composition that contains the additive of the composition that maybe will be exposed to the iodine hydrocarbon compound.Therefore, in described composition, do not require to have the iodine hydrocarbon compound, and require to exist aforesaid dialkylene compound.In a preferred embodiment, stabiliser composition of the present invention comprises the combination of dialkylene compound and at least a additional stability agent, described additional stability agent is selected from the group that is made up of above-mentioned additional stability agent, preferably is selected from the group that is made up of the combination of phenolic compound, epoxy compounds, phosphorous acid ester, phosphoric acid ester and these materials.

VI. method and system

Composition of the present invention is suitable for using in conjunction with several different methods and system, comprises as the heat-transfer fluid in heat-transferring method and the system, for example is used for freezing, the refrigeration agent of air-conditioning and heat pump.The present invention also is advantageously used in the system and method that produces aerosol, preferably comprises described aerosol propellant or be made up of described aerosol propellant in described system and method.Some aspect of the present invention also comprises method and the fire extinguishing and the method that suppresses flame that forms foam.In some aspects, the present invention also provides from composition of the present invention and be used as the method for removing resistates in the object of solvent compositions described method and system.

A. heat-transferring method

Preferred heat-transferring method generally comprises provides composition of the present invention and the preferred phase by changing composition and/or make heat be delivered to composition or transmit out from composition by appreciable heat transfer.For instance, method of the present invention preferably provides cooling by near evaporation refrigerant composition of the present invention entity to be cooled or fluid with the steam that generation comprises the present composition by absorbing heat from fluid or object.Method of the present invention preferably includes another step of compress refrigerant vapor, compresses to produce the steam of the present composition under relatively high pressure with compressor or similar devices usually.In general, the step of compressed vapour causes that the steam heat increases, thereby promotes the temperature of relatively high pressure steam.Preferably, method of the present invention comprises from described relatively-high temperature, high compressed steam and removes the heat of part at least that is increased by evaporation and compression step.Heat eliminating step preferably includes and makes high temperature, high compressed steam condensation that steam is under the relatively high pressure condition, comprises the relatively high pressure liquid of the present composition with generation.Preferably this relatively high pressure liquid then experiences nominal constant enthalpy reduction reaction under the pressure to produce relative low temperature, low pressure liquid.In described embodiment, then by the described low-temperature refrigerant liquid of the heat of vaporization that entity or fluid to be cooled transmitted.

In other method embodiment of the present invention, composition of the present invention can be used for producing in the method for heat, and described method makes the condensation of refrigerant that comprises described composition near being included in liquid to be heated or entity.Method as indicated above often is the reverse circulation of above-mentioned refrigeration cycle.

B. foaming method

A kind of embodiment of the present invention relates to the formation foam and is preferably urethane and the method for poly-isocyanurate foaming body.Know as affiliated field, described method generally comprises provides foaming agent composotion of the present invention, in foaming composition (directly or indirectly) add this foaming agent composotion, and foaming composition is reacted under the condition that can form foam or polynuclear plane.Any method of knowing in the affiliated field, for example " Polyurethanes Chemistry andTechnology ", I volume and II volume, Saunders and Frisch, 1962, John Wiley and Sons, New York, the method described in the NY (incorporating this paper by reference into) can be used for or is applicable among the foam embodiment of the present invention.In general, described preferred method comprises by with isocyanic ester, polyvalent alcohol or polyol blends, whipping agent or comprise the blowing agent blends of one or more present compositions and other material (for example catalyzer, tensio-active agent and optionally fire retardant, tinting material or other additive) combination prepares urethane or poly-isocyanurate foaming body.

In the prescription that in many application, easily the described component of urethane or poly-isocyanurate foaming body is provided in to be pre-mixed.The most frequently used is that the foam prescription is pre-mixed into two kinds of components.Isocyanic ester and optional some tensio-active agent and whipping agent constitute first component, so-called " A " component.Polyvalent alcohol or polyol blends, tensio-active agent, catalyzer, whipping agent, fire retardant and other isocyanate-reactive component constitute second component, so-called " B " component.Thus, by manual mixing (small-sized preparation) and preferably the subsidiary component of A and B is mixed and easily prepare urethane or poly-isocyanurate foaming body to form block, plate, veneer sheet, cast-in-place plate and other project, spray coating foaming body, bubble etc. by the mechanically mixing technology.Optionally can add other composition (for example fire retardant, tinting material, whipping agent even other polyvalent alcohol) as the 3rd stream that flows to mixing head or reactive site.Also can optionally described various composition parts be added in the B component, and a part is as the 3rd stream that flows to mixing head or reactive site.Yet, most preferably as mentioned above all the components is all incorporated in the B component.

Also may use the thermoplastic expanded body of composition production of the present invention.For example, the polystyrene of routine and polyethylene prescription and described composition can be made up in a usual manner and produce the rigidity foam.

C. purging method

The present invention also provides by object being used the method that composition of the present invention is removed pollutent from product, part, assembly, substrate or any other object or its part.For simplicity, term used herein " object " is meant all described products, part, assembly, substrate etc., and is used for representing its arbitrary surface or part in addition.In addition, term " pollutent " is used to represent existing any unwanted material or material on the object, even described material is to have a mind to be placed on the described object.For example, when making semiconductor device, often photoresist is deposited to and form the etching operation mask on the substrate and then remove described photoresist from substrate.Term " pollutent " comprises and contains such photoresist as used herein.

The preferred method of the present invention comprises composition of the present invention is applied on the object.Though expect that many various cleaning techniques can adopt the present composition to reach good advantage, think and especially advantageously use composition of the present invention in conjunction with overcritical cleaning technique.United States Patent (USP) the 6th, 589 discloses overcritical cleaning technique in No. 355 (transferred the assignee of the present invention, and incorporated this paper by reference into).Use for overcritical cleaning, preferably in cleaning combination of the present invention, except HFO-1234 (being preferably HFO-1234ze), also comprise one or more annexing ingredients in certain embodiments, for example CO ₂With other known annexing ingredient that uses of using in conjunction with overcritical cleaning.In certain embodiments, also may and need use cleaning combination of the present invention in conjunction with special vapor degreasing and solvent cleaning method, described vapor degreasing and solvent cleaning method are particularly preferred for some is used, and especially relate to complicated shape and the application that is difficult to scrubbing.Preferred vapor degreasing and solvent cleaning method comprise preferably and at room temperature object are exposed in the steam of boiling solvent.The advantage that steam condensation on object has provides clean relatively, solvent distillation is washed greasy dirt or other pollutent off.Therefore, the added benefit of described method is solvent compositions of the present invention finally evaporation from the object, stays and only compares relative resistates seldom with the situation of liquid solvent washing object.

Comprise the application of the pollutent that is difficult to remove for object, preferably the inventive method comprises the temperature increase of solvent compositions of the present invention to more than the envrionment temperature or rise to any other temperature of effectively improving the solvent cleaning effect in described application substantially.Described method also is preferred for jumbo fabrication line operation usually, and in described fabrication line operation, the cleaning of the cleaning of object, especially metal parts and assembly parts must effectively and fast be finished.

In a preferred embodiment, purging method of the present invention comprises in object immersion high temperature (and even more preferably from about under boiling temperature of the solvent) liquid solvent to be cleaned.In described operation, this step is preferably removed quite a large amount of from object, and even more preferably most target contaminant.Preferably then described object is immersed in the solvent after this step, preferably immerse in the fresh distillatory solvent, solvent temperature is lower than the temperature of liquid solvent in the last impregnation steps, preferably about envrionment temperature or room temperature.Preferable methods also comprises the step of the steam contact that then makes the relative heat with solvent compositions of the present invention of object, preferably by make object be exposed to by with the relevant solvent vapour of mentioning for the first time that heat/boiling solvent produced of impregnation steps.This preferably causes solvent vapour condensation on object.In some preferred embodiment, available solvent distillation sprays object, carries out final flushing afterwards.

The many modification and the type of expection vapor degreasing equipment are suitable for using in conjunction with the inventive method.People such as Sherliker disclose an example of this kind equipment and its operation at United States Patent (USP) the 3rd, 085 in No. 918 (incorporating this paper by reference into).The disclosed equipment of people such as Sherliker comprises the boiling pool that is used to hold solvent compositions, the service sink that is used to hold solvent distillation, water separator and other utility appliance.

Purging method of the present invention also can comprise cold rinse, wherein contaminated object immersed in the fluid composition of the present invention under envrionment temperature or room temperature condition, or under the described conditions with the rag or the similar object wiping that are immersed in the solvent.

Some preferred purging method comprises with composition flushing substrate of the present invention.

D. reduce flammable method

According to some other preferred embodiment, the invention provides and reduce the flammable method of fluid, described method comprises and add compound of the present invention or composition in described fluid.Can reduce the combustibility relevant according to the present invention with multiple flammable fluid.For example, can reduce according to the present invention and the combustibility relevant as oxyethane, flammable hydrogen fluorohydrocarbon and hydro carbons fluids such as (comprising HFC-152a, 1,1,1-Halothane (HFC-143a), methylene fluoride (HFC-32), propane, hexane, octane etc.).For example, some composition of the present invention can comprise CF ₃I and HFC-152a are by the gross weight of described two kinds of components, CF ₃The degree of I is greater than 0% to about 38.5%, and more preferably greater than 0% to about 35%, and the degree of HFC-152a is about 61.5% to less than 100%, and even more preferably from about 65% to less than about 100%.For realizing purpose of the present invention, flammable fluid can be any fluid that shows in air by the measured flammability range of any conventional criteria test method (for example ASTM E-681 etc.).

The The compounds of this invention or the composition that can add any appropriate amount reduce fluidic combustibility of the present invention.Recognize that as the those skilled in the art amount of adding is depending on that to the small part degree combustibility that flammable degree of target fluidic and expectation reach reduces degree.In some preferred embodiment, join the compound in the flammable fluid or the amount of composition and can produce non-flammable substantially fluid.

E. flame inhibition method

The present invention provides the method that suppresses flame in addition, and described method comprises makes flame contact with the fluid that comprises The compounds of this invention or composition.Any appropriate method that can use flame to contact with the present composition.For example, can the present composition be applied on the flame, at least a portion of flame is immersed in the composition by modes such as injection, cast.According to the instruction of this paper, the those skilled in the art should be able to be used for the present invention with various conventional flame restraining devices and method.

F. sterilising method

Many objects, device and material, the object, device and the material that are particularly useful for medical field are being used for the necessary before process sterilization of health and secure context (for example health and the safety of patient and hospital self).The invention provides sterilising method, comprise object subject to sterilization, device or material are contacted with compound of the present invention or composition.Described method can be high temperature or low temperature sterilization.In certain embodiments, high-temperature sterilization comprises makes object subject to sterilization, device or material arrive under the temperature of about 270  at about 250 , preferably is exposed to the hot-fluid that comprises The compounds of this invention or composition in the cell of sealing substantially.This process can be finished being less than in about 2 hours time usually.But some object (for example plastic article and electronic package) can not bear described high temperature, and needs temperature sterilization.

Temperature sterilization of the present invention is included in about 100  and uses compound of the present invention or composition under the temperature of about 200 .Compound of the present invention can combine with other common chemical disinfectant (for example comprising oxyethane (EO), formaldehyde, hydrogen peroxide, dioxide peroxide and ozone), forms microbicide composition of the present invention.

The two-step approach that temperature sterilization of the present invention preferably carries out in (preferred resistance to air loss) cell of sealing substantially.In the first step (sterilization steps), the object that cleans and wrap up is placed described cell in venting bags.Then by vacuumizing, perhaps by come the air in the emptying cell with steam replacement air.In certain embodiments, preferably in cell injecting steam reach preferred relative humidity between about 30% to about 70%.Described humidity can make the sterilization of disinfectant render a service maximization, and disinfectant is introduced in the cell after reaching desired relative humidity.Through after being enough to make disinfectant infiltration lapping and arriving the time period in object gap, discharge disinfectant and steam from cell.

In preferred second step (aeration step) of described method, object is ventilated to remove the disinfectant resistates.Though it is optionally in the situation of non-toxic compound substantially that resistates is removed using the present invention, particularly important in the situation of toxicity disinfectant.Typical method of ventilation comprises the combination of air scour (air wash), continuous ventilating and two kinds of methods.Air scour is a batch process, comprise usually through short period (for example 12 minutes) emptying cell, and then barometric point or more under the high pressure in cell introducing air.Repeat this circulation arbitrary number of times, remove degree up to reaching required disinfectant.Continuous ventilating generally includes the inlet introducing air via cell one side, and then applies slight underpressure by the outlet to the cell opposite side and give off the air of being introduced through outlet.These two kinds of methods often are used in combination.For example, common methods comprises advanced line space gas flushing, the circulation of then ventilating again.

G. stabilization method

The present invention provides the stable method for compositions that comprises iodine hydrocarbon (for example CF3I) in addition.The preferable methods step comprises provides at least a iodine hydrocarbon compound, and makes it stable by making described at least a iodine hydrocarbon compound be exposed to dialkylene compound of the present invention.In many examples, providing the step of iodine hydrocarbon to comprise provides a kind of composition (composition that comprises above-mentioned particular type) and add dialkylene compound of the present invention in described composition, and this adds preferred the mixing with described iodocarbon compositions by the stabiliser composition of the present invention with significant quantity and finishes.

H. supercritical process

Expect that multiple use as herein described and method generally can be with being in overcritical or realizing near the present composition of supercritical state.For example, composition of the present invention can be used in solvent mentioned in this article and the solvent extraction application, especially use in conjunction with for example following material: alkaloid (deriving from plant usually), for example caffeine (caffeine), morphine monomethyl ether (codeine) and Papaverine (papaverine); The organo-metallic material, for example metallocene (metallocene) generally is used as catalyzer; And spices and essence, for example jasmone.

Composition of the present invention (preferably be in overcritical or near the composition of postcritical state) can be in conjunction with comprising that the method that catalyzer (especially organo-metallic catalyst) is deposited on the solid carrier uses.In a preferred embodiment, described method comprises preferably by making catalyst particle from being in overcritical or precipitating the step that produces the finely powdered catalyst particle near the present composition of supercritical state.In some preferred embodiment, wish the good activity of catalyzer displaying prepared according to the methods of the invention.

Expect that also some MDI method and apparatus as herein described can utilize the medicine of finely powdered form, and in some cases, expection the invention provides comprise preferred by finely powdered medicine particle (for example salbutamol (albuterol)) is dissolved in preferably be in overcritical or near in the present composition of supercritical state with the method for the step in the described particle introducing fluid of the present invention.Under the relatively low situation of described substance dissolves degree, when fluid of the present invention is in overcritical or during near supercritical state, can preferably uses for example entrainment agent of alcohols.

Also expection is in overcritical or can be used for cleaning circuit plate and other electronic material and object near the present composition of supercritical state.

The solubleness of some material in the present composition may be very limited, especially is in overcritical or during near supercritical state when the present composition.For this type of situation, composition of the present invention can make described low solubility solute another kind of overcritical or form precipitation near the solution the supercritical solvent (for example carbonic acid gas) from being in as anti-solvent.For example, in the extrusion process of thermoplastic expanded body, often use supercritical co, and composition of the present invention can be used for precipitating some wherein contained material.

Also expection in certain embodiments, may need to use be in overcritical or near the present composition of supercritical state as whipping agent.

Example

Further explain the application's case according to following example, these examples only are illustrative, and do not wish to be limited by any way.

Example 1

The explanation of this example comprises CF ₃The stable composition of the present invention of I, PAG oil and isoprene.

The mixture of CF3I (25% (weight percent)) and HFO-1234yf (75% (weight percent)) (1.6 gram) joined to contain weight percent be that 3 of 99%PAG oil and 1% isoprene restrains in the compositions.The gained mixture placed have aluminium, the glass test tube of steel and copper tinsel, and then test tube is sealed.The baking oven of the sealing glass test tube being put into 300  lasted for 2 weeks.Shift out test tube subsequently and observe.

During observation, mixture is a phase, and showing that refrigeration agent keeps during this period can be miscible and be dissolvable in water in the PAG oil.In addition, the liquid in the test tube is transparent light yellow.Steel disc does not change.

Open glass test tube and extract gas.By the existence of trifluoromethane (HFC-23) in the vapor-phase chromatography detected gas, trifluoromethane (HFC-23) is that oil reacts the degradation production that produces with the trifluoro iodide.The weight percent content of HFC-23 is about 0.23 ± 0.07%.

Example 2

The explanation of this example comprises CF ₃The stable composition of the present invention of I, PAG oil and myrcene.

The mixture of CF3I (25% (weight percent)) and HFO-1234yf (75% (weight percent)) (1.6 gram) joined to contain weight percent be that 3 of 99%PAG oil and 1% myrcene restrains in the compositions.The gained mixture placed have aluminium, the glass test tube of steel and copper tinsel, and then test tube is sealed.The baking oven of the sealing glass test tube being put into 300  lasted for 2 weeks.Shift out test tube subsequently and observe.

During observation, mixture is a phase, and showing that refrigeration agent keeps during this period can be miscible and be dissolvable in water in the PAG oil.In addition, the liquid in the test tube is transparent light yellow.Steel disc does not change.

Open glass test tube and extract gas.By the existence of trifluoromethane (HFC-23) in the vapor-phase chromatography detected gas, trifluoromethane (HFC-23) is that oil reacts the degradation production that produces with the trifluoro iodide.The weight percent content of HFC-23 is 0.27%.Repeated experiments, and the result is the HFC-23 of 0.28% (weight percent).

Example 3

The explanation of this example comprises CF ₃The stable composition of the present invention of I, PAG oil and farnesol.

The mixture of CF3I (25% (weight percent)) and HFO-1234yf (75% (weight percent)) (1.6 gram) joined to contain weight percent be that 3 of 99%PAG oil and 1% farnesol restrains in the compositions.The gained mixture placed have aluminium, the glass test tube of steel and copper tinsel, and then test tube is sealed.The baking oven of the sealing glass test tube being put into 300  lasted for 2 weeks.Shift out test tube subsequently and observe.

During observation, mixture is a phase, and showing that refrigeration agent keeps during this period can be miscible and be dissolvable in water in the PAG oil.In addition, the liquid in the test tube is transparent light yellow.Steel disc does not change.

Open glass test tube and extract gas.By the existence of trifluoromethane (HFC-23) in the vapor-phase chromatography detected gas, trifluoromethane (HFC-23) is that oil reacts the degradation production that produces with the trifluoro iodide.The weight percent content of HFC-23 is 0.16%.

Example 4

The explanation of this example comprises CF ₃The stable composition of the present invention of I, PAG oil and Geraniol.

The mixture of CF3I (25% (weight percent)) and HFO-1234yf (75% (weight percent)) (1.6 gram) joined to contain weight percent be that 3 of 99%PAG oil and 1% Geraniol restrains in the compositions.The gained mixture placed have aluminium, the glass test tube of steel and copper tinsel, and then test tube is sealed.The baking oven of the sealing glass test tube being put into 300  lasted for 2 weeks.Shift out test tube subsequently and observe.

During observation, mixture is a phase, and showing that refrigeration agent keeps during this period can be miscible and be dissolvable in water in the PAG oil.In addition, the liquid in the test tube is transparent light yellow.Steel disc does not change.

Open glass test tube and extract gas.By the existence of trifluoromethane (HFC-23) in the vapor-phase chromatography detected gas, trifluoromethane (HFC-23) is that oil reacts the degradation production that produces with the trifluoro iodide.The weight percent content of HFC-23 is 0.14%.

Example 5

The explanation of this example comprises CF ₃I, polyalkylene glycol lubricant and myrcene and triphenyl phosphite (available from the DP213 of DoverChemical) are as the stable composition of the present invention of oil additive.The weight percent content of every kind of additive in oil is 0.5%.

The mixture of CF3I (about 9% (weight percent)) and HFO-1234yf (about 91% (weight percent)) (1.6 gram) joined to contain weight percent be that 99% polyalkylene glycol lubricant (buying with Motorcraft PAGRefrigerant Compressor Oil) and 1% restrains in the compositions as 3 of additive as described in the epimere.The gained mixture placed have aluminium, the glass test tube of steel and copper tinsel, and then test tube is sealed.The baking oven of the sealing glass test tube being put into 300  lasted for 2 weeks.Shift out test tube subsequently and observe.

During observation, mixture is a phase, and showing that the iodine hydrocarbon compound keeps during this period can be miscible and be dissolvable in water in the PAG oil.In addition, the liquid in the test tube is transparent light yellow.Steel disc does not change.

Open glass test tube and extract gas.By the existence of HFC-23 in the vapor-phase chromatography detected gas, HFC-23 is that oil reacts the degradation production that produces with the trifluoro iodide.The weight percent content of HFC-23 is about 0.2%.

Example 6

The explanation of this example comprises CF ₃The stable composition of the present invention of I and polyalkylene glycol lubricant and the stablizer formed by myrcene.

CF3I (1.6 gram) is joined 3 grams contain in the polyalkylene glycol lubricant of myrcene, wherein by the gross weight of lubricant, the weight percent content of myrcene is 1%.The gained mixture placed have aluminium, the glass test tube of steel and copper tinsel, and test tube sealed.The baking oven of the sealing glass test tube being put into 300  lasted for 2 weeks.Shift out test tube subsequently and observe.

During observation, mixture is a phase, shows that refrigeration agent can be miscible and be dissolvable in water in the PAG oil.In addition, the liquid in the test tube is transparent light yellow.Steel disc does not change.

Open glass test tube and extract gas.By the existence of trifluoromethane (HFC-23) in the vapor-phase chromatography detected gas, trifluoromethane (HFC-23) is that oil reacts the degradation production that produces with the trifluoro iodide.The weight percent content of HFC-23 is 0.23%.

Example 7

This example explanation is by being used in combination the additive myrcene and Doverphos DP 213 sharply reduces CF ₃The degree of decomposition of I in mineral oil.

The mixture (1.6 gram) of CF3I (25% (weight percent)) and HFO-1234yf (75% (weight percent)) is joined in the 3 gram mineral oil.Contain weight percent in the mineral oil and be 0.5% myrcene and 0.5% Doverphos DP-213.The gained mixture placed have aluminium, the glass test tube of steel and copper tinsel, and then test tube is sealed.The baking oven of the sealing glass test tube being put into 300  lasted for 2 weeks.Shift out test tube subsequently.

Open glass test tube and extract gas.By the existence of trifluoromethane (HFC-23) in the vapor-phase chromatography detected gas, trifluoromethane (HFC-23) is that oil reacts the degradation production that produces with the trifluoro iodide.The weight percent content of HFC-23 is 0.08%.Repeated experiments and result are the HFC-23 of 0.08% (weight percent).

Comparative example 1

The mixture of CF3I (about 9% (weight percent)) and HFO-1234yf (about 91% (weight percent)) (1.6 gram) joined contain in the 3 gram compositions that weight percent is 99% polyalkylene glycol lubricant (buying with Motorcraft PAGRefrigerant Compressor Oil).Do not use stabilizer additive.The gained mixture placed have aluminium, the glass test tube of steel and copper tinsel, and then test tube is sealed.The baking oven of the sealing glass test tube being put into 300  lasted for 2 weeks.Shift out test tube subsequently and observe.

During observation, mixture is a phase, and showing that refrigerant composition keeps during this period can be miscible and be dissolvable in water in the mineral oil.After the exposure, tinsel fades and the color of lubricant is a dark-brown.

Open glass test tube and extract gas.By the existence of HFC-23 in the vapor-phase chromatography detected gas, HFC-23 is that oil reacts the degradation production that produces with the trifluoro iodide.The weight percent content of HFC-23 is about 1.0%.

Comparative example 2

The mixture (1.6 gram) of CF3I (25% (weight percent)) and HFO-1234yf (75% (weight percent)) is joined in the 3 gram mineral oil.The gained mixture placed have aluminium, the glass test tube of steel and copper tinsel, and then test tube is sealed.The baking oven of the sealing glass test tube being put into 300  lasted for 2 weeks.

Open glass test tube and extract gas after exposing for two weeks.By the existence of trifluoromethane (HFC-23) in the vapor-phase chromatography detected gas, trifluoromethane (HFC-23) is that oil reacts the degradation production that produces with the trifluoro iodide.The weight percent content of HFC-23 is 0.76%.Repeated experiments and result are the HFC-23 of 1.51% (weight percent).

Claims (84)

1. heat transfer compositions, it comprises:

(a) at least a iodine hydrocarbon (iodocarbon); With

(b) at least a dialkylene (diene-based) compound, its content stablize described at least a iodine hydrocarbon effectively in case degraded.

2. heat transfer compositions according to claim 1, wherein said at least a iodine hydrocarbon comprises at least a iodine fluorohydrocarbon.

3. heat transfer compositions according to claim 2, wherein said at least a iodine fluorohydrocarbon comprises at least a C1-C3 iodine fluorohydrocarbon.

4. heat transfer compositions according to claim 3, wherein said at least a C1-C3 iodine fluorohydrocarbon comprises CF ₃I.

5. heat transfer compositions according to claim 4, wherein said at least a C1-C3 iodine fluorohydrocarbon is basically by CF ₃I forms.

6. heat transfer compositions according to claim 1, wherein said at least a dialkylene compound comprises isoprene.

7. heat transfer compositions according to claim 1, wherein said at least a dialkylene compound comprises propadiene.

8. heat transfer compositions according to claim 1, wherein said at least a dialkylene compound comprises at least a isoprene based compound.

9. heat transfer compositions according to claim 1, wherein said at least a dialkylene compound comprises at least a terpenyl compound.

10. heat transfer compositions according to claim 9, wherein said terpenyl compound are myrcene (myrcene).

11. heat transfer compositions according to claim 9, wherein said terpenyl compound are farnesol (farnesol).

12. heat transfer compositions according to claim 9, wherein said terpenyl compound are Geraniol (geraniol).

13. heat transfer compositions according to claim 1, wherein said at least a dialkylene compound is present in the described composition with about 0.0001 amount to about 30 weight percents.

14. heat transfer compositions according to claim 1, it comprises at least a non-iodine hydrocarbon coolant compound in addition.

15. heat transfer compositions according to claim 14, wherein said at least a non-iodine hydrocarbon coolant compound comprises at least a HF hydrocarbon.

16. heat transfer compositions according to claim 15, wherein said at least a HF hydrocarbon comprise at least a hydrogen fluorine propylene.

17. heat transfer compositions according to claim 16, wherein said at least a hydrogen fluorine propylene comprises at least a tetrafluoeopropene (HFO-1234).

18. heat transfer compositions according to claim 14, wherein said at least a non-iodine hydrocarbon coolant compound comprises at least a hydrogen fluorohydrocarbon.

19. heat transfer compositions according to claim 1, it has and is not more than about 100 global warming potential.

20. heat transfer compositions according to claim 1, it comprises at least a lubricant in addition.

21. heat transfer compositions according to claim 20, wherein said lubricant are selected from the group that is made up of following each thing: two or more combination in naphthenic mineral oil, paraffin mineral oil, ester oil, polyalkylene glycol, polyvinyl ether, alkylbenzene, polyalphaolefin and the described material.

22. heat transfer compositions according to claim 1, wherein said at least a iodine hydrocarbon comprises the CF3I that accounts for exhausted vast scale by weight.

23. a composition that contains the iodine hydrocarbon, it is stabilized in case carbon-iodine bond decomposes, and it comprises:

(a) at least a iodine hydrocarbon; With

(b) at least a dialkylene compound, its amount stablizes described at least a iodine hydrocarbon effectively in case degraded.

24. the method for conducting heat in fluid or entity or outwards conducting heat from fluid or entity, it comprises makes described fluid or entity contact with the composition that comprises composition according to claim 23.

25. composition according to claim 23, it has and is not more than about 150 global warming potential (GWP).

26. composition according to claim 23, it has and is not more than about 0.05 ozone depletion latent energy value (ODP).

27. an obturator-type foam, it comprises the polymer foaming body prescription that comprises whipping agent, and described whipping agent comprises composition according to claim 23.

28. a foam Preblend composition, it comprises composition according to claim 23.

29. the method for a stable composition, it comprises provides the composition that contains the iodine hydrocarbon and described composition is contacted with the dialkylene compound.

30. a heat transfer compositions, it comprises:

(a) at least a formula I fluoroolefin:

XCF _zR _3-z(I)，

Wherein X is the alkyl that C2 or C3 are unsaturated, be substituted or be unsubstituted, and R is Cl, F, Br, I or H independently, and z is 1 to 3;

(b) at least a iodine hydrocarbon.

31. heat transfer compositions according to claim 30, wherein said at least a fluoroolefin are formula II compound:

Wherein each R is Cl, F, Br, I or H independently,

R ' is (CR ₂) _nY,

Y is CRF ₂,

And n is 0 or 1.

32. heat transfer compositions according to claim 31, wherein said iodine hydrocarbon comprises CF ₃I.

33. heat transfer compositions according to claim 32, it has and is not more than about 1000 global warming potential (GWP).

34. heat transfer compositions according to claim 32, wherein said at least a fluoroolefin comprises at least a tetrafluoeopropene (HFO-1234).

35. heat transfer compositions according to claim 34, wherein said at least a HFO-1234 comprises HFO-1234yf.

36. heat transfer compositions according to claim 35, it comprises by HFO-1234yf and CF ₃The combination weight meter about 5 of I is to the HFO-1234yf of about 99 weight percents.

37. heat transfer compositions according to claim 35, it comprises by HFO-1234yf and CF ₃The combination weight meter about 50 of I is to the HFO-1234yf of about 95 weight percents.

38. heat transfer compositions according to claim 35, it comprises by HFO-1234yf and CF ₃The combination weight meter about 65 of I is to the HFO-1234yf of about 75 weight percents.

39. heat transfer compositions according to claim 35, it comprises by HFO-1234yf and CF ₃The HFO-1234yf of about 70 weight percents of combination weight meter of I and the CF of about 30 weight percents ₃I.

40. according to the described heat transfer compositions of arbitrary claim among the claim 30-39, it comprises diene or dialkylene stablizer in addition.

41. according to the described heat transfer compositions of claim 40, wherein by the gross weight of described composition, described stablizer exists with 0.001 amount to about 15 weight percents.

42. according to the described heat transfer compositions of claim 41, wherein by the gross weight of described composition, described stablizer exists with about 0.01 amount to about 10 weight percents.

43. according to the described heat transfer compositions of claim 42, wherein by the gross weight of described composition, described stablizer exists with about 0.3 amount to about 5 weight percents.

44. according to the described heat transfer compositions of claim 43, wherein by the gross weight of described composition, described stablizer exists with about 1 amount to about 2 weight percents.

45. an automobile refrigerating agent, it comprises according to the described composition of claim 40.

46. a refrigerator working fluid, it comprises according to the described composition of claim 40.

47. a working fluid that is used for Rankine cycle (Rankine-cycle) operation, it comprises according to the described composition of claim 40.

48. a working fluid that is used for organic Rankine cycle operation, it comprises according to the described composition of claim 40.

49. composition according to claim 23, wherein said composition are used as stabilized fluid in the product that is selected from the group that is made up of following each thing: foam, the thermoset foam, whole skin foam, foam Preblend, whipping agent, pressurization bubble foam (pressurized froth foam), solvent, cleaning solvent, extract solvent, aerosol, propelling agent, the fire extinguishing auxiliary agent, tensio-active agent, flush fluid, quantitative inhalation, lubricant, fire inhibitor, therapeutic composition, insecticides, herbicidal composition, oligopolymer and polymkeric substance.

50. a heat transfer compositions, it comprises iodine fluorohydrocarbon and at least a compound that is selected from the group that is made up of following each thing: methylene fluoride (HFC-32), pentafluoride ethane (HFC-125), 1,1,2,2-Tetrafluoroethane (HFC-134), 1,1,1,2-Tetrafluoroethane (HFC-134a), C2H4F2 C2H4F2 (HFC-152a), 1,1,1,2,3,3,3-heptafluoro-propane (HFC-227ea), 1,1,1,3,3,3-HFC-236fa (HFC-236fa), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-3-pentafluorobutane (HFC-365mfc), water, CO ₂With two or more combination in the described compound.

51. according to the described heat transfer compositions of claim 50, wherein said iodine hydrocarbon comprises CF ₃I.

52. according to claim 50 or 41 described heat transfer compositions, it comprises one or more lubricant in addition.

53. according to the described heat transfer compositions of claim 52, it comprises one or more lubricant in addition, the amount of described lubricant is that about 30 of described heat transfer compositions arrives about 50 weight percents.

54. the method for the existing refrigeration agent that an alternative refrigerant system is contained, it comprises at least a portion that substitutes existing refrigeration agent described in the described system, and by in described system, introducing at least a portion that the refrigerant composition that comprises at least a iodine hydrocarbon compound and at least a formula I fluoroolefin substitutes described existing refrigeration agent:

XCF _zR _3-z(I)，

Wherein X is the alkyl that C2 or C3 are unsaturated, be substituted or be unsubstituted, and R is Cl, F, Br, I or H independently, and z is 1 to 3.

55. according to the described method of claim 54, wherein said existing refrigeration agent comprises HFC-134a.

56. according to the described method of claim 54, wherein said existing coolant system is a refrigerator system.

57. according to the described method of claim 54, wherein said formula I fluoroolefin comprises HFO-1234yf.

58. according to the described method of claim 57, the weight percent content of wherein said HFO-1234yf in described refrigerant composition is about 5% to about 95%.

59. according to the described method of claim 54, wherein said existing coolant system comprises automotive air-conditioning system.

60. a foaming composition, it comprises foamable polymer or prepolymer and whipping agent, and described whipping agent comprises at least a formula I fluoroolefin:

XCF _zR _3-z(I)，

Wherein X is the alkyl that C2 or C3 are unsaturated, be substituted or be unsubstituted, and R is Cl, F, Br, I or H independently, and z is 1 to 3, and described whipping agent comprises at least a iodine hydrocarbon compound in addition.

61. according to the described foaming composition of claim 60, it has and is not more than about 1000 global warming potential (GWP).

62. a foam, it is made by the described foaming composition of claim 60.

63. a foam Preblend composition, it comprises polymkeric substance or prepolymer and whipping agent, and described whipping agent comprises iodine hydrocarbon compound and at least a formula I fluoroolefin:

XCF _zR _3-z(I)，

Wherein X is the alkyl that C2 or C3 are unsaturated, be substituted or be unsubstituted, and each R is Cl, F, Br, I or H independently, and z is 1 to 3, described foam ....

64. a whipping agent, it comprises composition according to claim 23.

65. a foaming composition, it comprises composition according to claim 23.

66. a heat transfer compositions, it comprises:

(a) at least a iodine hydrocarbon;

(b) hydrogen fluorohydrocarbon; With

(c) at least a dialkylene stablizer.

67. according to the described heat transfer compositions of claim 66, wherein said hydrogen fluorohydrocarbon comprises the isomer of C2H4F2 C2H4F2.

68. according to the described heat transfer compositions of claim 67, wherein said C2H4F2 C2H4F2 comprises HFC-152a.

69. according to the described heat transfer compositions of claim 68, wherein said iodine hydrocarbon comprises CF ₃I.

70., wherein press HFC-152a and CF according to the described heat transfer compositions of claim 69 ₃The gross weight meter of I, described HFC-152a exists with about 20 amounts to about 40 weight percents, and presses HFC-152a and CF ₃The gross weight meter of I, described CF ₃I exists with about 60 amounts to about 80 weight percents.

71., wherein press HFC-152a and CF according to the described heat transfer compositions of claim 70 ₃The gross weight meter of I, described HFC-152a exists with the amount of about 25 weight percents, and presses HFC-152a and CF ₃The gross weight meter of I, described CF ₃I exists with the amount of about 75 weight percents.

72. according to the described heat transfer compositions of claim 71, wherein by the gross weight of described composition, described stablizer exists with about 0.001 amount to about 15 weight percents.

73. according to the described heat transfer compositions of claim 72, wherein by the gross weight of described composition, described stablizer exists with about 0.01 amount to about 10 weight percents.

74. according to the described heat transfer compositions of claim 73, wherein by the gross weight of described composition, described stablizer exists with about 0.3 amount to about 5 weight percents.

75. according to the described heat transfer compositions of claim 74, wherein by the gross weight of described composition, described stablizer exists with about 1 amount to about 2 weight percents.

76. an automobile refrigerating agent, it comprises according to the described composition of claim 75.

77. an automobile refrigerating system, it comprises according to claim 76 or the described refrigeration agent of claim 45.

78. a refrigerator working fluid, it comprises according to the described composition of claim 75.

79. a working fluid that is used for the Rankine cycle operation, it comprises according to the described composition of claim 75.

80. a working fluid that is used for organic Rankine cycle operation, it comprises according to the described composition of claim 75.

81. according to the described composition of claim 49, it comprises HF hydrocarbon in addition, and wherein said iodine hydrocarbon comprises CF ₃I.

82. 1 described composition according to Claim 8, wherein said HF hydrocarbon comprises HFO-1234yf.

83. according to the described composition of claim 49, it comprises the hydrogen fluorohydrocarbon in addition and wherein said iodine hydrocarbon comprises CF ₃I.

84. 3 described compositions according to Claim 8, wherein said hydrogen fluorohydrocarbon comprises HFC-152a.